A New Interlaboratory Characterisation of Silicon,Rare Earth Elements and Twenty‐Two Other Trace Element Concentrations in the Natural River Water Certified Reference Material SLRS‐6 (NRC‐CNRC)

The natural river water reference material SLRS‐6 (NRC‐CNRC) is the newest batch of a quality control material routinely used in many international environmental laboratories. This work presents a nine‐laboratory compilation of measurements of major and trace element concentrations and their related uncertainties, unavailable in the NRC‐CNRC certificate (B, Cs, Li, Ga, Ge, Hf, Nb, P, Rb, Rh, Re, S, Sc, Se, Si, Sn, Th, Ti, Tl, W, Y, Y, Zr and REEs). Measurements were mostly made using inductively coupled plasma‐mass spectrometry. The results are compared with equivalent data for the last batch of the material, SLRS‐5, measured simultaneously with SLRS‐6 in this study. In general, very low concentrations, close to the quantification limits, were found in the new batch. The Sr isotopic ratio is also reported.     

Late glacial and early Holocene hydroclimate variability in northwest Iran (Talesh Mountains) inferred from chironomid and pollen analysis

We reconstructed the paleohydrologic and climatic history of the Lake Neor region, NW Iran, from the end of the late glacial to the middle Holocene (15,500–7500 cal yr BP). Subfossil chironomid and pollen assemblages in a sediment core from a peatland located south of Lake Neor enabled identification of four main hydrologic phases. The period 15,500–12,700 cal yr BP was characterized by a relatively dry climate with an open landscape, suggested by the abundance of Irano-Turanian steppe plants (e.g. Amaranthaceae, Artemisia and Cousinia). Dominance of several shallow-water and semi-terrestrial chironomid taxa (e.g. Pseudosmittia, Smittia/Parasmittia and Paraphaenocladius/Parametriocnemus) during this period is indicative of lower water tables in the wetland. Between 12,700 and 11,300 cal yr BP, chironomid taxa indicate higher wetland water tables, as suggested by the presence of Zavrelia, Chironomus anthracinus/plumosus-type and Micropsectra, which are inhabitants of open-water, lacustrine areas. The open-steppe vegetation remained dominant in the watershed during this time. Increasing wetland moisture could be explained by: (1) cool summers that reduced the evaporation rate; and/or (2) a decrease in duration of the summer dry season. The period 11,300–8700 cal yr BP was characterized by lower wetland moisture, contemporaneous with a delay in the expansion of deciduous forest, suggesting persistent dry climate conditions throughout the beginning of the Holocene, which may have been related to the intensified seasonality of precipitation. Around 8700 cal yr BP, higher wetland water levels, inferred from chironomids, occurred simultaneously with the onset of regional deciduous forest expansion, probably caused by a shortening of the summer dry period. We concluded that chironomids are appropriate paleoecological proxies to investigate global and local hydrologic variability in the Middle East.     

Baseline determination of the atmospheric Pb,Sr and Nd isotopic compositions in the Rhine valley,Vosges mountains (France) and the Central Swiss Alps

The Pb, Sr and Nd isotopic compositions of biomonitors (lichen, moss, bark) and soil litter from different regions in the Rhine valley, as well as of <0.45 μm particles separated out of ice of the Rhône and Oberaar glaciers and lichens from the Swiss Central Alps, have been determined in order to deduce the natural baseline of the atmospheric isotopic compositions of these regions, which are suggested to be close to the isotopic compositions of the corresponding basement rocks or soils at the same sites. ²⁰⁶Pb/²⁰⁷Pb and ⁸⁷Sr/⁸⁶Sr isotope ratios are positively correlated. Most polluted samples from traffic-rich urban environments have the least radiogenic Pb and Sr isotopic compositions with ²⁰⁶Pb/²⁰⁷Pb and ⁸⁷Sr/⁸⁶Sr ratios of 1.11 and 0.7094, respectively. These ratios are very different from those of the atmospheric baseline for the Vosges mountains and the Rhine valley (²⁰⁶Pb/²⁰⁷Pb: 1.158–1.167; ⁸⁷Sr/⁸⁶Sr: 0.719–0.725; ε_Nd: −7.5 to −10.1). However, this study indicates that the baseline of the atmospheric natural Pb and Sr isotopic compositions is affected by anthropogenic (traffic, industrial and urban) emissions even in remote areas. Lichen samples from below the Rhône and Oberaar glaciers reflect the baseline composition close to the Grimsel pass in the Central Swiss Alps (⁸⁷Sr/⁸⁶Sr: 0.714 − 0.716; ε_Nd: −3.6 to −8.1). The ¹⁴³Nd/¹⁴⁴Nd isotope ratios are highly variable (8ε units) and it is suggested that the variation of the ¹⁴³Nd/¹⁴⁴Nd is controlled by wet deposition and aerosols originating from the regional natural and industrial urban environments and from more distant regions like the Sahara in North Africa. The least anthropogenetically affected samples collected in remote areas have isotopic compositions closest to those of the corresponding granitoid basement rocks.     

Comparative behaviour of recently deposited radiostrontium and atmospheric common strontium in soils (Vosges mountains,France)

The vertical distribution of atmospheric ⁸⁷Sr/⁸⁶Sr isotope ratios in soil is compared to the distribution of recent atmospheric ⁹⁰Sr deposition. ⁸⁷Sr/⁸⁶Sr isotope ratios of soil leachates are correlated with ⁹⁰Sr activities. Samples from the uppermost part of a soil profile have low ⁸⁷Sr/⁸⁶Sr ratios and high ⁹⁰Sr activities. Samples from the deeper part of the soil profile, however, have high ⁸⁷Sr/⁸⁶Sr but low ⁹⁰Sr activities. This points to mixing between an atmospheric and a geogenic component. Mixing calculations indicate that 50–80% of the Sr in the topsoil of a small catchment in the Vosges mountains is of atmospheric origin. Similarly ⁸⁷Sr/⁸⁶Sr of roots point to the presence of an atmospheric and geogenic component. ⁸⁷Sr/⁸⁶Sr ratios of soil leachates and corresponding roots are very similar indicating, that the roots integrate at each level of the soil profile the leachable Sr of the corresponding soil.     

Statistical downscaling in the arid central Andes: uncertainty analysis of multi-model simulated temperature and precipitation

Statistical downscaling is a technique widely used to overcome the spatial resolution problem of General Circulation Models (GCMs). Nevertheless, the evaluation of uncertainties linked with downscaled temperature and precipitation variables is essential to climate impact studies. This paper shows the potential of a statistical downscaling technique (in this case SDSM) using predictors from three different GCMs (GCGM3, GFDL and MRI) over a highly heterogeneous area in the central Andes. Biases in median and variance are estimated for downscaled temperature and precipitation using robust statistical tests, respectively Mann?CWhitney and Brown?CForsythe's tests. In addition, the ability of the downscaled variables to reproduce extreme events is tested using a frequency analysis. Results show that uncertainties in downscaled precipitations are high and that simulated precipitation variables failed to reproduce extreme events accurately. Nevertheless, a greater confidence remains in downscaled temperatures variables for the area. GCMs performed differently for temperature and precipitation as well as for the different test. In general, this study shows that statistical downscaling is able to simulate with accuracy temperature variables. More inhomogeneities are detected for precipitation variables. This first attempt to test uncertainties of statistical downscaling techniques in the heterogeneous arid central Andes contributes therefore to an improvement of the quality of predictions of climate impact studies in this area.     

High resolution LA-ICP-MS mapping of U and Th isotopes in an early Pleistocene equid tooth from Fuente Nueva-3 (Orce, Andalusia, Spain)

We have produced detailed maps of U and Th isotopes for three cross-sections of an Early Pleistocene equid tooth from the archaeological site of Fuente Nueva-3 (Orce, Andalusia, Spain). This permits us to visualise, for the first time, U migration processes in 3 dimensions. The tooth shows a concentration gradient from the top to the base, indicating the U profile had not equilibrated after >1 Ma. The spatial pattern of ²³⁰Th/²³⁴U and ²³⁴U/²³⁸U indicates complex U-mobilisation processes over the last 100 ka, dominated by small-scale redistribution of U. Leaching from the tooth through the pulp cavity started at least 93 ka ago with several later phases in various domains of the dentine and cement. This leaching event could have been triggered by changes in the local hydrological regime associated with periods of increased erosion in the Guadix-Baza basin. The results illustrate the difficulty of dating faunal material from Early Pleistocene sites. They also demonstrate that dental tissues can neither be considered as homogeneous media for U-diffusion, nor behave as closed systems for U-series isotopes because diagenetic alterations seem to trigger U-migration. The results do not support the notion that U-uptake into dental tissues is necessarily of short duration. Nevertheless, rapid laser ablation scanning can be used to identify suitable samples for dating as well as domains within the teeth that may have preserved original isotopic signatures, i.e. domains that have not been affected by recent U-mobilisation process.     

Line-broadening effects in the powder infrared spectrum of apatite

The crystallinity of natural and synthetic apatite samples is often determined from the broadening of ν ₄ PO₄ infrared absorption bands. However, various physical mechanisms contribute to the observed linewidth. In the present study, the factors determining the linewidth in the powder spectrum of synthetic fluorapatite and hydroxyapatite samples are investigated. The temperature dependence of the infrared spectrum (10–270 K) is used to assess the respective contributions of homogeneous broadening, related to the decay of phonons through anharmonic coupling, and heterogeneous broadening related to elastic strain and macroscopic electrostatic effects. This latter contribution is dominant in the investigated samples and depends on the shape of powder particles. It is discussed under the light of the theoretical modeling of the low-frequency dielectric properties of apatite based on first-principles density functional theory calculations. The linewidth of the weak ν ₁ PO₄ absorption band provides a reliable information on microscopic sources of broadening, i.e., apatite crystallinity. In comparison, the other more intense PO₄ bands are more sensitive to long-range electrostatic effects.     

La méthode SHYREG débit—application sur 1605 bassins versants en France métropolitaine

Résumé

La méthode SHYREG est une approche développée pour la connaissance régionale de l’aléa pluvial (SHYREG pluie) et hydrologique (SHYREG débit) en tout point du territoire français. Elle est basée sur le couplage d’un générateur stochastique de pluie horaire et d’un modèle hydrologique. Cet article présente les résultats de la mise en ?uvre de la méthode sur 1605 bassins versants répartis sur la France métropolitaine. Sur les fréquences courantes (c.à.d. périodes de retour inférieures à 10 ans), la méthode restitue correctement les quantiles de débit de crue ajustés à une loi statistique sur les observations (loi GEV, selon le critère de Nash-Sutcliffe). Plusieurs critères sont utilisés pour valider l’extrapolation des débits à des fréquences extrêmes: (a) en la confrontant à de longues chroniques de débits observés, (b) en analysant dans le modèle hydrologique la saturation du réservoir de production synonyme de comportement asymptotique avec les pluies, et (c) en étudiant la stabilité de la méthode à travers les critères statistiques.

Editeur Z.W. Kundzewicz; Editeur associé G. Mahé

Citation Aubert, Y., Arnaud, P., Ribstein, P., et Fine, J.-A., 2014. La méthode SHYREG débit, application sur 1605 bassins versants en France Métropolitaine. Hydrological Sciences Journal, 59 (5), 993–1005.